Aqueous surface-treating agent

ABSTRACT

An aqueous surface-treating agent, which comprises a silicone oil aqueous emulsion, a polyurethane resin aqueous emulsion, and a silane compound represented by the following general formula: 
     
       
         
         
             
             
         
       
     
     (where R 1  and R 2  each are an alkyl group having 1 to 4 carbon atoms, and n and m are 1≦n≦3 and m=3−n, respectively), and/or a hydrolyzate thereof; wherein 100 parts by weight or more of the polyurethane resin in terms of the weight of solid matters is used on the basis of 100 parts by weight in terms of nonvolatile matters of silicone oil, can prevent sticking of rubber seal materials such as O rings, etc. themselves or sticking to a metal, a resin, etc., and can reduce the friction of rubber or resin seal members at the time of sliding motion.

RELATED APPLICATION

This application is a continuation application of U.S. patentapplication Ser. No. 12/681,919, filed Apr. 7, 2013 which in turn was a35 U.S.C. §371 national phase filing of International Patent ApplicationNo. PCT/JP2008/062994, filed Jul. 18, 2008. Priority is claimed under 35U.S.C. §120 to U.S. patent application Ser. No. 12/681,919 and toInternational Patent Application No. PCT/JP2008/062994. Priority isfurther claimed under 35 U.S.C. §119 to Japanese Patent Application Nos.2007-263457, filed Oct. 9, 2007 and 2008-164431, filed Jun. 24, 2008.

TECHNICAL FIELD

The present invention relates to an aqueous surface-treating agent, andmore particularly to an aqueous surface-treating agent effectivelyapplicable to surfaces of rubber seal materials, etc.

BACKGROUND ART

Most of now available rubber seal materials suffer from stickingproblems between seal materials themselves or sticking to contactsurfaces of mating materials such as metals, resins, etc., whenassembled into equipment. To overcome such problems, a liquid materialsuch as wax, grease, lubricating oil, etc. is applied to the sealmaterials, thereby improving the assembling work.

When rubber parts such as O rings, etc. are transported by a partsfeeder to conduct automatic assembling, the more the liquid material isapplied, the lower the friction coefficient, but blocking of the partsthemselves will occur due to sticking of the applied liquid material,thereby bringing about an inconvenience to the automatic feeding of theparts. To reduce the sticking occurrence, on the other hand, the lessthe liquid material to be applied, the more often the liquid material isliable to deposit onto the surroundings, thereby causing the blocking.The applied liquid material is liable to come off due to the liquidnature, and thus its retainability is not sufficient. Furthermore, it isdifficult to control the application amount of the liquid material, andthus it is difficult to obtain the rubber parts in a stable state onlyby the liquid material. Blocking as well as sticking can be prevented byspraying inorganic powders of graphite, silica, talc, etc., butsurrounding pollution due to disengagement of the deposited powders isinevitable.

To overcome such problems, Patent Document 1 proposed a surface-treatingagent, which comprises (1) a reaction product of polysiloxane having aterminal hydroxyl group, with silyl isocyanate, (2) a reaction productof an oligomer having a functional group reactive with an isocyanategroup, with silyl isocyanate, (3) a silyl isocyanate oligomerrepresented by the following general formula:

(R: an alkyl group, an aryl group, or an isocyanate group, and n: aninteger of 1 or more), and (4) an organic solvent-soluble rubber. Theassembling work and stickiness can be improved by such asurface-treating agent, but the major component of the surface-treatingagent is an organic solvent such as toluene, ethyl acetate, methyl ethylketone, etc., which can also lead to such problems as a highenvironmental load and a difficult handling.

Patent Document 1: JP-A-2000-63744

Patent Document 2 proposes an aqueous mold-releasing agent compositionfor use upon application to the surface of a mold, which comprises (A) asilicone emulsion, (B) a urethane resin-based aqueous emulsion, and (C)a silane compound having at least one of epoxy group andmethacryloxypropyl group at the molecular chain terminal, and/or apartial hydrolyzate thereof. Such a composition has a low environmentalload due to the aqueous system, but has a problem of surroundingpollution due to bleeding of oily matters onto the surface afterapplication and drying, when used as a surface-treating agent for thesliding members, which is the object of the present invention, becausethe aqueous emulsion containing a polyhydrazide and a carbonylgroup-containing polyurethanevinylhybrid polymer is used as Component(B). Furthermore, tight adhesion to the rubber materials is notsatisfactory, resulting in short durability and easy peeling. Thus, theproposed composition is not preferable.

Patent Document 2: JP-A-2005-125656

DISCLOSURE OF THE INVENTION Problem to be Solved by the Invention

The object of the present invention is to provide an aqueoussurface-treating agent capable of preventing sticking between rubberseal materials such as O rings, etc. themselves or sticking to metals,resins, etc., and reducing friction of rubber or resin seal members atthe time of sliding motion.

Means for Solving the Problem

The object of the present invention can be attained by an aqueoussurface-treating agent, which comprises a silicone oil aqueous emulsion,a polyurethane resin aqueous emulsion, and a silane compound representedby the following general formula:

(where R¹ and R² each are an alkyl group having 1-4 carbon atoms, n andm are 1≦11≦3 and m=3−n, respectively), and/or a partial hydrolyzatethereof, wherein 100 parts by weight or more, preferably 100-2,000 partsby weight, of the polyurethane resin in terms of the weight of solidmatters is used on the basis of 100 parts by weight in terms of theweight of nonvolatile matters of the silicone oil.

Effect of the Invention

The present surface-treating agent has such features as a lowenvironmental load owing to the nature of an aqueous system and a goodapplicability without any special equipment. Furthermore, the tightadhesion to substrates can be attained without any bleeding of oilymatters by making the total polyurethane resin content higher than thesilicone oil content, whereby a distinguished durability can beobtained. As a result, sticking between rubber materials such as 0 ringsthemselves or sticking to metals, resins, etc. can be effectivelyprevented, and furthermore friction of rubber or resin seal members canbe reduced at the time of sliding motion.

When a mixture of (a) an aqueous emulsion containing a hydrazide and acarbonyl group-containing polyurethane resin and (b) an aqueous emulsionof a silanol-modified polyurethane resin is used as the polyurethaneresin, the solvent resistance can be also improved in addition to theafore-mentioned features.

BEST MODES FOR CARRYING OUT THE INVENTION

The silicone oil for use in the present invention includes anorganopolysiloxane having at least one organic group bonded to thesilicon atom and having a kinematic viscosity at 25° C. of 50-1,000,000mm²/sec., preferably 500-200,000 mm²/sec., where its molecular structurecan be any of linear, branched or reticular structures, preferablylinear or branched one, more preferably linear one. The organic groupbonded to the silicon atom of organopolysiloxane is typically an alkylgroup such as methyl, ethyl, propyl, butyl, or hexyl; an alkenyl groupsuch as vinyl, or propenyl; an aryl group such as phenyl; an aralkylgroup such as phenethyl; and those hydrocarbon groups, some of whosehydrogen atoms are substituted by a halogen atom, a nitrile group, etc.The terminal organic group of organopolysiloxane is typically methyl,amino, epoxy, carbinol, hydroxyl, methoxy, methacryloxy, carboxyl,silanol, alkoxy, etc., and preferably carbinol, hydroxyl or methoxy. Thesilicone oil can give a lubricability, a low friction, and anon-stickiness to the surface-treatment film.

The aqueous emulsion containing such a silicone oil for use in thepresent invention includes not only a hydrophilic type silicone oilaqueous emulsion, but also an emulsifier-forced emulsion type siliconeoil aqueous emulsion, where their dispersion method is not particularlylimited. Such silicone oil aqueous emulsions have a silicone oil content(nonvolatile matters) of 3-60 wt. %.

The silicone oil aqueous emulsion is admixed with a predetermined amountof a polyurethane resin aqueous emulsion. Polyurethane resin (solidmatters) is added to the silicone oil aqueous emulsion in a proportionof 100 parts by weight or more, preferably 100-2,000 parts by weight, onthe basis of 100 parts by weight of silicone oil (nonvolatile matters)of the silicone oil aqueous emulsion. When the polyurethane resin isused in a proportion of less than 100 parts by weight, the coatabilitywill be lowered, and bleeding of silicone oil will occur to lower thedurability. Thus, this is not preferable.

The polyurethane resin aqueous emulsion includes a self-emulsificationtype having hydrophilic groups as introduced into the polyurethanestructure, a forced emulsification type emulsified by an emulsifier,etc., where any type of polyurethane molecular structure, such as etherpolyol type, ester polyol type, polycarbonate type, etc. can be usedwithout any particular limitation. It is preferable to use an aqueousemulsion containing a hydrazide and a carbonyl group-containingpolyurethane resin as a self cross-linkable type polyurethane, and morepreferable to use a mixture thereof further with a silanol-modifiedpolyurethane resin aqueous emulsion or with a self cross-linkablegroup-free polyurethane resin aqueous emulsion, particularly preferablya mixture thereof further with a silanol-modified polyurethane resinaqueous emulsion. In the case of the mixture thereof further with thesilanol-modified polyurethane resin aqueous emulsion, it is preferableto prepare the mixture upon mixing in a ratio by weight of solid mattersum total of the aqueous emulsion containing a hydrazide and carbonylgroup-containing polyurethane resin silanol-modified polyurethaneresin=5-90:95-10. In the case of the mixture thereof further with theself cross-linkable group-free polyurethane resin aqueous emulsion, thesame solid matter ratio by weight as mentioned above can be used.

The self cross-linkable type polyurethane has more distinguished solventresistance, tight adhesion, and stability than those of the selfcross-linkable group-free polyurethane resin, and thus even in the caseof using only the aqueous emulsion containing a hydrazide and a carbonylgroup-containing polyurethane resin, the afore-mentioned characteristicscan be fully obtained by making total content of polyurethane resinhigher than the silicone oil content. The silanol-modified, selfcross-linkable type polyurethane can attain much higher levels ofsolvent resistance and tight adhesion. Thus, a polyurethane resinaqueous emulsions surface-treating agent comprising a mixture of thesecomponents can reduce the friction of rubber or resin seal members atthe time of sliding motion, and also can improve the solvent resistance.The silanol groups as contained therein have a good compatibility withsilicone oil and silane compound as constituents of the aqueoussurface-treating agent. This is another advantage of using thesilanol-modified polyurethane resin aqueous emulsion.

The aqueous emulsion containing a hydrazide and a carbonylgroup-containing polyurethane resin includes an aqueous emulsioncontaining a hydrazide and a carbonyl group-containingpolyurethanevinylhybrid polymer, as disclosed in Patent Documents 3and 4, where the azomethine bonds formed by reaction of the hydrazidewith the carbonyl group of polyurethane-vinyl-hybrid polymer can lead tocross-linking. In this case, these two compounds can be used generallyin a proportion of the number of hydrazine groups to the number ofcarbonyl groups of 1:40-2:1.

The hydrazide includes hydrazine, lower molecular weight aliphaticcompound, aromatic compound or mixture thereof having a hydrazide groupand/or a hydrazone group, and further includes a polyhydrazide or apolyvalent hydrazide compound having at least two of these groups. Thepolyurethane-vinyl-hybrid polymer can be prepared by freeradical-initiated polymerization of an ionically and/or nonionicallystabilized polyurethane macromonomer having a terminal vinyl groupand/or side chain vinyl group, and in some cases a terminal hydroxylgroup, a urethane group, a thiourethane group or a urea group, withother functional vinyl monomer having a carbonyl group, and anon-functional vinyl monomer. For such aqueous emulsion, commerciallyavailable products, such as Daotan VTW6462/36WA, a product of JapanThytec Industries, Daotan series, products of Solucia Japan, etc. can bepractically used, as described in afore-mentioned Patent Document 2.

Patent Document 3: JP-A-7-233347

Patent Document 4: JP-A-2006-299274

The silanol-modified polyurethane resin aqueous emulsion is an aqueousdispersion containing silanol groups in the polyurethane structure,where the silanol groups turn to siloxane bonds by condensationcross-linking reaction:

The siloxane bonds are stable, as compared with bonds formed by otherurethanization cross-linking reaction, and thus the resulting surfacetreatment film has such an effect as a good solvent resistance. Thepolyurethane resin aqueous emulsion can give a sliding durability to thesurface treatment film, and further can take the silicone oil therein togive a lubricability, a low frictional resistance, and a non stickiness,without any bleeding the oil matters to the surface treatment film. Thesilanol-modified polyurethane resin aqueous emulsion for use herein hasa resin concentration of 10-70 wt. % in terms of solid matters.

The silane compound for use herein includes silane compounds representedby the following general formula:

H₂N(CH₂)₃Si(OR¹)nR² m,  (D)

or

H₂NC₂H₄NH(CH₂)₃Si(OR¹)nR² m  (E)

(R1, R2 an alkyl group having 1-4 carbon atoms, n, m 1≦n≦3, m=3−n).These silane compounds are components capable of holding the siliconeoil within the surface treatment film by reaction of the reactiveorganic groups of the silicone emulsion with the alkoxy groups of theafore-mentioned specific silane compounds, and capable of giving alubricability, a low friction resistance, and a non-stickiness of thesurface, without any bleeding the oily matters, and also reacting withthe polyurethane aqueous emulsion to improve the affinity betweencross-linked polyurethane resin and the silicone oil to retain thesilicone oil within the surface treatment film. Furthermore, thesesilane compounds can act to improve the coatability on a substrate to besurface treated.

Such silane compounds include, for example,γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,γ-glycidoxypropyltripropoxysilane,γ-glicidoxypropylmethyldimethoxysilane,γ-glycidoxypropylmethyldiethoxysilane,γ-glicidoxypropylmethyl-dipropoxysilane, (i.e. silane compounds A);γ-methacryloxypropyltrimethoxysilane,γ-methacryloxypropyltriethoxysilane,γ-methacryloxy-propyltripropoxysilane,γ-methacryloxypropylmethyldimethoxysilane,γ-methacryloxypropylmethyldiethoxysilane,γ-methacryloxypropylmethyl-dipropoxysilane (i.e. silane compound B);3-acryloxypropylmethyl-dimethoxysilane,3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropyl-triethoxysilane(i.e. silane compounds C); 3-aminopropyltrimethoxysilane,3-aminopropyltriethoxysilane (i.e. silane compounds D); andN-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane,N-2-(aminoethyl)-3-aminopropyltrimethoxysilane,N-2-(aminoethyl)-3-aminopropyltriethoxysilane,3-(2-aminoethyl)-aminopropylmethyldimethoxysilane (i.e. silane compoundsE), among which γ-glycidoxypropyltrimethoxysilane,γ-glycidoxypropylmethyldimethoxysilane,γ-methacryloxypropyltrimethoxysilane,γ-methacryloxypropylmethyldimethoxysilane, etc. can be preferably used.

Partial hydrolyzates of these silane compounds can be also used in thepresent invention. The hydrolyzates can be obtained by condensationreaction of one of the silane compounds or a mixture of two or morethereof, under hydrolysis conditions depending on the species of theselected silane compounds.

It is preferable to add 10-60 parts by weight of the silane compound to100 parts by weight of oily matters (nonvolatile matters) of siliconeoil emulsion. When the silane compound is used in a proportion of morethan 60 parts by weight, the friction coefficient will be increased, andthe durability will be lowered, whereas in a proportion of less than 10parts by weight, excess bleeding of oil will occur.

To prevent thread-forming spinnability or partial liquid gathering,thereby stopping occurrence of a potted coating or short coating amount,the surface-treating agent comprising above-mentioned, essentialcomponents can contain an amphoteric surfactant such as alkylamineoxide-based compounds, alkyl betaine, etc. The alkylamine oxide-basedcompounds include dimethylalkylamine oxide, etc., and the alkyl betaineincludes alkyldimethylaminoacetic acid betaine, etc., where the alkylgroup includes, for example, lauryl group, myristyl group, naturaloil-modified groups derived from coconut oil, etc. The alkylamineoxide-based compound or the alkyl betaine can be used in a proportion of10 wt. % or less on the basis of total composition.

The surface-treating agent can further contain a defoaming agent, apigment, inorganic powders, a thickening agent, a surfactant, etc., ifrequired. The composition is used upon dilution with water to aconcentration of the effective components to 0.1-40 wt. % from theviewpoint of coating efficiency and coatability. These compoundingingredients are used upon mixing and emulsification treatment withsufficient stirring. The mixing can be carried out by a well-knownmixer-stirrer, a combi-mix, etc. provided with stirring blades of paddletype, anchor type, etc., and the emulsification treatment can be carriedout by an emulsifyingdispersing device such as a colloid mill, ahomo-mixer, a homogenizer, a sand grinder, etc.

The surface-treating agent so prepared can be subjected to surfacetreatment by applying it to the surface of a member to be coated byimmersion, brush coating, roll coating, spray coating, knife coating,dip coating, etc., followed by heat drying at 120°-150° C. for 30-60minutes to form a cured film.

The present surface-treating agent can be effectively used for rubbermaterials such as fluororubber, NBR, hydrogenated NBR, SBR, isoprenerubber, butadiene rubber, chloroprene rubber, acrylic rubber, EPDM,urethane rubber, silicone rubber, etc., or for resin materials such asthermoplastic resins, thermosetting resins, etc., for example, ABS, AS,etc.

EXAMPLES

The present invention will be described in detail below, referring toExamples.

Parts by weight Both terminal hydroxyl groups-containing emulsion4.07(1.34) polymerization polydimethylsiloxane aqueous emulsion(viscosity at 25° C.: 100,000 mPa · sec; nonvolatile matters: 33%)Hydrazide and carbonyl group-containing polyurethane 2.71(0.98) resinaqueous emalsion (solid matters 36 wt. %; Daotan VTW 6462/36WA)Silanol-modified polyurethane resin aqueous emulsion 6.67(2.00) (solidmatters: 30 wt. %; Tackelack WS-5000, a product of Mitsui ChemicalPolyurethane Co.) γ-glycidoxypropyltrimethoxysilane 0.68Dimethyllaurylamine oxide (amphoteric surfactant) 0.45 Water 85.42The foregoing components (figures in the parentheses show weights ofsolid matters) were mixed together, and further subjected toemulsification treatment by a homogenizer and an ultrasonic treatingunit to obtain a surface-treating agent. The resulting surface-treatingagent had 2.98 parts by weight of total polyurethane resins, whichcorresponded to 222.3 parts by weight on the basis of 100 parts byweight of silicone oil (in terms of nonvolatile matters, as will belikewise used hereinafter).

Then, the surface-treating agent was applied to a fluororubber sheet anda fluororubber O ring (hardness: JIS A70 dimensions: 7.8 mm in innerdiameter, 1.9 mm in thickness (diameter), and nominal number: JIS B2401-4 grade D P8 by spray costing method), and then cured at 150° C.for 30 minutes to obtain the coated fluororubber sheet and O ring eachhaving a coating film as formed thereon to a film thickness of about 2μm.

The surface treated fluororubber sheet having a thickness of 2 mm or Oring was subjected to determination and tests according to the followingtest items:

Friction coefficient: According to ASTM D-1894 determine kinematicfriction coefficient of surface-treated, vulcanized rubber sheet surfaceby using a surfaceness tester, Heydon tribogear, made by ShintoScientific Co.

(Test Conditions)

Mating member: SUS304 steel ball, 10 mm in diameter

Moving speed: 50 mm/min.

Load: 0.49N

Amplitude: 50 mm

Durability test: To conduct a test under the following conditions, usinga Heydon tribogear, and then evaluate the tested film states accordingto the following ranking:

No peeling: O

Partial exposure of the substrate: X

(Test Conditions)

Mating member: SUS304 steel ball, 10 mm in diameter

Moving speed: 400 mm/min.

Load: 0.98N

Amplitude: 30 mm by 500 runs

Non-stickiness test: To conduct a test by sandwiching thesurface-treated fluororubber O ring between SUS430 members, followed byheating in a thermostat tank at 150° C. in a 50% compressed state for 30minutes, leaving to stand at room temperature for one hour, releasingthe O ring from the SUS members, and then to evaluate the releasingstate according to the following ranking:

-   -   Immediately releasable from the mold without any trouble: O    -   Sticky right after the leasing operation, but releasable from        the mold one minute thereafter: Δ    -   Sticky or peeling by transfer to the SUS members: X

Solvent resistance test: To immerse the surface-treated fluororubber Oring into toluene for 24 hours, then conduct as ultrasonic washertreatment for 10 minutes, while keeping the O ring as immersed intoluene, then taking it out of the toluene, and evaluate the film stateaccording to the following ranking:

Neither dissolution nor peeling of the film: O

Neither dissolution nor peeling, but whitening of the film: Δ

Observation of either dissolution or peeling of the film: X

Bleeding evaluation: To apply the surface-treating agent to a rubbersheet, followed by drying, and evaluate the surface state of thesurface-treated rubber sheet according to the following ranking:

No bleeding of oily matters to the surface: O

Bleeding of oil matters to the surface: X

Pot life test: To leave a surface-treating agent solution having a solidmatter concentration of 10 wt. % to stand in the circumstance at theliquid temperature of 25° C. and the humidity of 70% for 72 hours andevaluate formation of precipitates in the solution by visual observationaccording to the following ranking:

No observation of precipitates: O

Observation of precipitates: X

Coatability test: To visually observe the coating film state ofsurface-treated fluororubber sheet to evaluate according to thefollowing ranking: Uniform coating without any unevenness: O

Uneven coating without uniform coating: X

Evaluation of O ring transporting characteristics by parts feeder: Totransport 500 surface-treated fluororubber O rings by a parts feeder,and count the number of passed O rings per hour (transport rate) and thenumber of O rings remaining on the parts feeder, where the more thepassed O rings number, the higher the transport rate, and the blocked Orings remain on the parts feeder

Example 2

In Example 1, the same amount of γ-methacryloxypropyltrimethoxysilanewas used in place of γ-glycidoxypropyltrimethoxysilane. The resultingsurface-treating agent had 2.98 parts by weight of total polyurethaneresins, which corresponded to 222.3 parts by weight on the basis of 100parts by weight of silicone oil.

Example 3

In Example 1, the same amount of a self-cross-linking group-freepolyurethane resin aqueous emulsion (solid matters 30 wt. %; TackelackW-6061, a product of Mitsui Chemical Polyurethane Co.) was used in placeof the silanol-modified polyurethane resin aqueous emulsion. Theresulting surface-treating agent had 2.98 parts by weight of totalpolyurethane resins, which corresponded to 222.3 parts by weight on thebasis of 100 parts by weight of silicone oil.

Example 4

In Example 1, the silanol-modified polyurethane resin aqueous emulsionwas excluded from use, and the amount of the hydrazide and carbonylgroup-containing urethane resin aqueous emulsion was changed to 8.28(2.98) parts by weight. The resulting surface-treating agent had 2.98parts by weight of total polyurethane resins, which corresponded to222.3 parts by weight on the basis of 100 parts by weight of siliconeoil.

Comparative Example 1

In Example 1, the following components were used for a surface-treatingagent

Parts by weight Both terminal hydroxyl groups-containing, emulsion2.30(0.76) polymerization polydimethylsiloxane aqueous emulsion(nonvolatile matters 33%) Hydrazide and carbonyl group-containingpolyurethane 1.55(0.56) resin aqueous emulsion (solid matters: 36 wt. %)γ-glycidoxypropyltrimethoxysilane 0.40 Dimethyllaurylamine oxide 0.75Water 95.00The resulting surface-treating agent had 0.56 parts by weight of totalpolyurethane resins, which corresponded to 73.5 parts by weight on thebasis of 100 parts by weight of silicone oil.

Comparative Example 2

In Comparative Example 1, the same amount ofγ-methacryloxypropyltrimethoxysilane was used in place of theγ-glycidoxypropyltrimethoxysilane. The resulting surface-treating agenthad 0.56 parts by weight of total polyurethane resins, whichcorresponded to 73.5 parts by weight on the basis of 100 parts by weightof silicone oil.

Comparative Example 3

In Comparative Example 1, neither hydrazide and carbonylgroup-containing polyurethane resin aqueous emulsion, norγ-glycidoxypropyltrimethoxysilane, and dimethyllaurylamine oxide wasused at all.

Comparative Example 4

In Example 1, no surface treatment was carried out at all.

The results obtained in the foregoing Examples and Comparative Examplesare shown in the following Table.

TABLE Example No. Comp. Ex. No. 1 2 3 4 1 2 3 4 Test items Frictioncoefficient 0.16 0.16 0.17 0.17 0.18 0.18 0.05 2.50 Durability test ◯ ◯◯ ◯ X X X — Non-stickiness tests ◯ ◯ Δ Δ ◯ ◯ ◯ X Solvent resistance test◯ ◯ X Δ Δ Δ X — Bleeding evaluation ◯ ◯ ◯ ◯ X X X — Pot life test ◯ ◯ ◯◯ ◯ ◯ ◯ — Coatability test ◯ ◯ ◯ ◯ X X X — Transport characteristicstest Transport rate 100 100 90 80 50 40 60 10 (number of O rings/min)Remaining O rings 0 0 10 10 100 110 200 300 (number) Overall evaluation◯ ◯ Δ Δ X X X X

It can be seen from the foregoing results that in the cases of lowfriction coefficient without any stickiness there are such tendenciesthat blocking and number of remaining 0 rings will be smaller, and thetransport rate will be higher, whereas in the case of application ofonly silicone oil or higher silicone oil content, stickiness will beincreased though the friction coefficient is lowered, resulting inblocking of O rings themselves, and slower transport rate.

INDUSTRIAL UTILITY

The present aqueous surface-treating agent can be effectively used forthe surface treatment of seal materials such as 0 rings, oil seals, Vrings, D rings, X rings, packings, etc., automobile sliding rubber suchas weather strips, wiper blades, etc., business machine rubber materialssuch as toner blades, rubber rolls, etc., resin gears for use inautomobiles, business machines, etc., and sliding members such aspaper-feeding resin clicks for printers, etc.

1-9. (canceled) 10: An aqueous surface-treating anti-adhesive agent,which comprises a silicone oil aqueous emulsion, a polyurethane resinaqueous emulsion, and a silane compound represented by the followinggeneral formula:

(where R¹ and R² each are independently an alkyl group having 1-4 carbonatoms, n and m are 1≦n≦3 and m=3−n respectively), and/or a partialhydrolyzate thereof, wherein 100 parts by weight or more of thepolyurethane resin in terms of the weight of solid matters is used onthe basis of 100 parts by weight in terms of the weight of nonvolatilematters of the silicone oil, wherein the polyurethane resin aqueousemulsion is a mixture of (a) an aqueous emulsion containing a hydrazideand a carbonyl group-containing polyurethane resin, and (b) asilanol-modified polyurethane resin aqueous emulsion wherein thesilanol-modified polyurethane resin has, in the polyurethane structure,silanol groups, which turn to siloxane bonds by condensationcross-linking reaction after surface treating, in a ratio by weight ofsolid matter sum total of (a):(b)=5-95:95-10, and wherein when appliedto rubber seal members the anti-adhesive agent prevents sticking of therubber seal members to themselves and prevents sticking of the rubberseal members to other materials. 11: An aqueous surface-treatinganti-adhesive agent according to claim 10, wherein 10-60 parts by weightof the silane compound and/or a hydrolyzate thereof is used on the basisof 100 parts by weight in terms of nonvolatile matters of the siliconeoil. 12: An aqueous surface-treating anti-adhesive agent according toclaim 10, for application to the surfaces of rubber materials or resinmaterials. 13: An aqueous surface-treating anti-adhesive agent accordingto claim 12, wherein the rubber materials are seal materials. 14: A sealmaterial surface-treated by an aqueous surface-treating anti-adhesiveagent according to claim
 13. 15: An aqueous surface-treatinganti-adhesive agent according to claim 12, wherein the rubber materialsare sliding members. 16: A sliding member surface-treated by an aqueoussurface-treating anti-adhesive agent according to claim
 15. 17: A methodfor surface-treating rubber materials to prevent sticking of the rubbermaterials to themselves and prevent sticking of the rubber materials toother materials which method comprises: a) providing an aqueoussurface-treating anti-adhesive agent, which comprises a silicone oilaqueous emulsion, a polyurethane resin aqueous emulsion, and a silanecompound represented by the following general formula:

(where R¹ and R² each are independently an alkyl group having 1-4 carbonatoms, n and m are 1≦n≦3 and m=3−n respectively), and/or a partialhydrolyzate thereof, wherein 100 parts by weight or more of thepolyurethane resin in terms of the weight of solid matters is used onthe basis of 100 parts by weight in terms of the weight of nonvolatilematters of the silicone oil, wherein the polyurethane resin aqueousemulsion is a mixture of (a) an aqueous emulsion containing a hydrazideand a carbonyl group-containing polyurethane resin, and (b) asilanol-modified polyurethane resin aqueous emulsion wherein thesilanol-modified polyurethane resin has, in the polyurethane structure,silanol groups, which turn to siloxane bonds by condensationcross-linking reaction after surface treating, in a ratio by weight ofsolid matter sum total of (a):(b)=5-95:95-10, and wherein when appliedto rubber seal members the anti-adhesive agent prevents sticking of therubber seal members to themselves and prevents sticking of the rubberseal members to other materials; and (b) surface-treating rubbermaterials with the aqueous surface-treating anti-adhesive agent.